EP1027348B1 - 2-(2'-hydroxyphenyl)benzotriazole verwendbar als uv-stabilisatoren - Google Patents

2-(2'-hydroxyphenyl)benzotriazole verwendbar als uv-stabilisatoren Download PDF

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EP1027348B1
EP1027348B1 EP19980955498 EP98955498A EP1027348B1 EP 1027348 B1 EP1027348 B1 EP 1027348B1 EP 19980955498 EP19980955498 EP 19980955498 EP 98955498 A EP98955498 A EP 98955498A EP 1027348 B1 EP1027348 B1 EP 1027348B1
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group
general formula
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hydroxyphenyl
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EP1027348A1 (de
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Rosa Maria Riva
Carlo Neri
Rosalba Colombo
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Lanxess Switzerland GmbH
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Great Lakes Chemical Europe GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to 2-(2'-hydroxyphenyl)benzotriazoles.
  • the present invention relates to 2-(2'-hydroxyphenyl)benzotriazoles containing a 2,4-imidazolidinedione group or a 2,4-imidazolidinedione-5,5-disubstituted group in the molecule, a process for their preparation and their use as light stabilizers for organic polymers.
  • the present invention also relates to the polymeric compositions stabilized with the above benzotriazoles and to the end-products obtained from these compositions.
  • EP-A-0 057 160 discloses 2-(2'-hydroxyphenyl-3'-tert.-butyl)benzotriazoles comprising a hydrocarbon chain which contains a carbonyl group and their use as UV stabilizers.
  • US Patent 4,077,971 discloses tetrahydrophthalimide methyl-2-phenylbenzatriazoles useful as ultraviolet absorbers.
  • US Patent 3,629,192, CH Patent 476 745 and FR Patent 1 324 899 disclose 2-(2'-hydroxyphenyl-)benzotriazoles comprising amine or amide groups. The compounds are said to act as light-stabilizers.
  • EP-A-0867435 disclosing 2-(2'hydroxyphenyl)benzotriazoles and their use as light stabilizers for organic polymers.
  • the benzotriazoles however have various disadvantages. In fact, they are often rather volatile, they have a low thermal stability and, as they sometimes have a significant absorption at 400 nm, they give the polymers, into which they are incorporated, a yellow colouring.
  • the present invention therefore relates to 2-(2'-hydroxyphenyl)benzotriazoles having general formula (I): wherein:
  • the compounds having general formula (I) can be used as light stabilizers for organic polymers.
  • the C 5 -C 18 cycloalkyl groups, the C 6 -C 14 aryl groups and the heterocyclic groups with 5 or 6 atoms are defined as being optionally substituted, these groups are substituted with: halogen atoms selected from chlorine and bromine, linear or branched C 1 -C 18 alkyl groups, linear or branched C 2 -C 18 alkenyl groups; linear or branched C 2 -C 18 alkynyl groups, OH groups, NH groups, SH groups.
  • C 1 -C 18 alkyl groups are: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, t-amyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-dodecyl, 1,1,7,7-tetramethyloctyl, n-octadecyl, etc.
  • C 2 -C 18 alkenyl groups are: vinyl, propylene, butylene, pentylene, hexylene, etc.
  • C 2 -C 18 alkynyl groups are: acetylene, propyne, butyne, 2-butyne, etc.
  • C 5 -C 18 cycloalkyl groups optionally substituted, are: cyclohexyl, cyclopentyl, methylcyciohexyl, etc.
  • C 7 -C 15 arylalkyl or alkylaryl groups are: benzyl, 2-phenylethyl, 4-t-butylbenzyl, etc.
  • C 6 -C 14 aryl groups optionally substituted, are: phenyl, naphthyl, anthracenyl, 2-hydroxyphenyl, etc.
  • C 1 -C 18 alkoxyl groups are: methoxyl, ethoxyl, propoxyl, n-butoxyl, etc.
  • heterocyclic groups with 5 or 6 atoms are: piperidine, morpholine, piperazine, triazole, tetramethylpiperidine, pentamethylpiperidine, tetramethylmorpholine, pentamethylmorpholine, 4-hydroxy-tetramethylpiperidine, etc.
  • the compounds having general formula (I) of the present invention can be prepared with various processes.
  • a further object of the present invention relates to a process for the preparation of 2-(2'-hydroxyphenyl)benzotriazoles having general formula (I).
  • a process for the preparation of compounds having general formula (I) comprises:
  • the 2-(2'-hydroxyphenyl)benzotriazoles having general formula (IX) can be prepared as described, for example, in German patent application DE 4.237.817.
  • the secondary amines having general formula (X) and 2,4-imidazolidinediones having general formula (XII), are commercially available compounds.
  • the compounds having general formula (I) of the present invention can be used as light stabilizers for a wide range of organic polymers.
  • Organic polymers capable of being stabilized with the compounds of the present invention are:
  • the compounds having formula (I) of the present invention are particularly useful in the stabilization of polycarbonates.
  • a further object of the present invention relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds having general formula (I).
  • the compounds having general formula (I) of the present invention can be used as such or combined with other stabilizers, in the above polymeric compositions.
  • the above compounds having general formula (I) are used in a quantity ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, although the quantity used varies according to the substrate to be stabilized and the final application. They are preferably added in a quantity ranging from about 0.5% to about 3% by weight of the weight of the polymeric compositions to be stabilized.
  • the compounds having general formula (I), optionally in the presence of other additives, can be easily incorporated in the organic polymers to be stabilized using the conventional techniques. This incorporation can take place before or during the formation of the end-product, for example, by mixing the compounds having general formula (I) in powder form with the polymer to be stabilized, or by adding these compounds to the polymer to be stabilized in the molten state or in solution, or applying a solution or suspension of these compounds to the polymer to be stabilized, optionally evaporating the solvent used.
  • the elastomers can be stabilized as latexes.
  • Another method for incorporating the compounds having general formula (I) in the organic polymers comprises the addition of these before or during the polymerization of the corresponding monomers or before the cross-linking.
  • the compounds having general formula (I) or their mixtures can be added to the polymer to be stabilized also in masterbatch form which comprises these compounds in a concentration ranging, for example, from 2.5% to 25% by weight.
  • the compounds having general formula (I) can be conveniently incorporated in the organic polymers to be stabilized by means of the following methods:
  • polymeric compositions stabilized as said above can be converted to end-products such as, for example, fibers, films, tapes, sheets, multi-layer sheets, containers, tubes and other forms, by means of methods known in the art such as, for example, casting, hot moulding, spinning, extrusion or injection moulding.
  • the present invention therefore also relates to the use of the above polymeric compositions for the production of end-products.
  • multi-layer systems in which one of the above compositions having a relatively high content of a compound having general formula (I), for example, between 5% and 15% by weight, is applied in the form of a thin film (10-100 ⁇ m in thickness) to a shaped article consisting of a polymer not containing or containing a small quantity of a compound having general formula (I).
  • This application can be carried out during the formation of said article, for example, by means of a co-extrusion.
  • the application can also be effected however on the end shaped-article, for example, by lamination with a film or by coating with a solution.
  • the surface layer or layers of the end-article act as a UV filter which protects the inside of the articles from the deteriorating action of UV light.
  • the upper layer preferably contains from 5% to 15% by weight, more preferably from 5% to 10% by weight, of at least one compound having general formula (I).
  • the polymers stabilized as described above have a high resistance to degradation caused by atmospheric agents, in particular a high resistance to UV light. They are therefore capable of maintaining their colour and brightness for a long period even when exposed to external agents.
  • compositions described above can also be used as compositions for coating or painting ("coating compositions") such as, for example, paints, lacquers, plastic-based compositions.
  • organic polymer is selected from:
  • thermoplastic polymers (a) containing heteroatoms, in particular nitrogen, sulfur and/or oxygen, in the main chain are listed above under points 13 to 20.
  • polycarbonates polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides are preferred; particularly preferred are polycarbonates, polyesters such as, for example, polyethylene terephthalate (PET), and polyamides (PA) such as, for example, PA 6 and PA 6/6; even more preferred are polycarbonates.
  • PET polyethylene terephthalate
  • PA polyamides
  • Paint ligands (b) can comprise at least one of the organic polymers specified herebelow. Specific examples of paints containing specific ligands are:
  • the paints can be applied as one or two layers of coating ("one- or two-coat") and the stabilizing compounds having formula (I) are preferably added to the upper colourless coating.
  • the paints can be applied to the substrate (metal, plastic, wood, etc.) using the conventional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis.
  • a preferred embodiment of the present invention consists in paints or coatings (for example car coatings) comprising at least one compound having general formula (I).
  • Ligands which can be used for the purpose are, for example, those listed above.
  • the compounds having general formula (I) of the present invention can be combined, as already mentioned above, with other conventional additives or their mixtures. These additives are added in a quantity ranging-from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example.
  • Films with a thickness of 100 ⁇ m are prepared from the above solutions by casting.
  • the films obtained are subjected to accelerated aging in an Atlas CI 65 Weatherometer under the following conditions:
  • the yellow index (YI) of the above films is measured using the method ASTM E 313. The crushing time is also analyzed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Cosmetics (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Claims (23)

  1. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I)
    Figure 00670001
       worin:
    X ein Wasserstoffatom, ein unter Chlor und Brom ausgewähltes Halogenatom, eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine geradekettige oder verzweigte C1-C18-Alkoxygruppe, eine Cyangruppe darstellt,
    R ein unter Chlor und Brom ausgewähltes Halogenatom, eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine geradekettige oder verzweigte C2-C18-Alkenylgruppe, eine geradekettige oder verzweigte C2-C18-Alkinylgruppe, eine C5-C18-Cycloalkylgruppe, wobei die Cycloalkylgruppe gegebenenfalls substituiert ist, eine C7-C15-Arylalkyl- oder Alkylaryl-Gruppe, eine C6-C14-Arylgruppe, wobei die Arylgruppe gegebenenfalls substituiert ist, eine geradekettige oder verzweigte C1-C18-Alkoxygruppe, eine heterocyclische Gruppe mit 5 oder 6 Atomen, die mindestens ein unter Sauerstoff, Stickstoff und Schwefel ausgewähltes Heteroatom enthält, wobei die heterocyclische Gruppe gegebenenfalls substituiert ist, eine Gruppe der Formel
    Figure 00680001
    eine -COR4-Gruppe oder eine -NR5R6-Gruppe darstellt, worin R4, R5 und R6 gleich oder verschieden sind und eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine geradekettige oder verzweigte C2-C18-Alkenylgruppe, eine geradekettige oder verzweigte C2-C18-Alkinylgruppe, eine C5-C18-Cycloalkylgruppe, die gegebenenfalls substituiert ist, darstellen, eine C7-C15-Arylalkyl- oder Alkylarylgruppe, eine C6-C14-Arylgruppe, wobei die Arylgruppe gegebenenfalls substituiert ist, eine heterocyclische Gruppe mit 5 oder 6 Atomen, die mindestens ein unter Sauerstoff, Stickstoff und Schwefel ausgewähltes Heteroatom enthält und wobei die heterocyclische Gruppe gegebenenfalls substituiert ist, darstellen,
    oder R eine Estergruppe der allgemeinen Formel (II), (III) oder (IV)
    Figure 00680002
    Figure 00680003
    Figure 00680004
    oder eine Amidgruppe der allgemeinen Formel (V)
    Figure 00690001
    darstellt,
    worin R' eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine geradekettige oder verzweigte C2-C18-Alkenylgruppe, eine geradekettige oder verzweigte C2-C18-Alkinylgruppe, eine C5-C18-Cycloalkylgruppe, wobei die Cycloalkylgruppe gegebenenfalls substituiert ist, eine C7-C15-Arylalkyl- oder Alkylarylgruppe, eine C6-C14-Arylgruppe, wobei die Arylgruppe gegebenenfalls substituiert ist, eine geradekettige oder verzweigte C1-C18-Alkoxygruppe, eine heterocyclische Gruppe mit 5 oder 6 Atomen, die mindestens ein unter Sauerstoff, Stickstoff und Schwefel ausgewähltes Heteroatom enthält, wobei die heterocyclische Gruppe gegebenenfalls substituiert ist, darstellt,
    oder R eine 4,4'-Ethylidenbisphenol-Gruppe der Formel (VI) darstellt:
    Figure 00690002
    R1 ein Wasserstoffatom, eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine geradekettige oder verzweigte C2-C18-Alkenylgruppe, eine geradekettige oder verzweigte C2-C18-Alkinylgruppe, eine C5-C18-Cycloalkylgruppe, wobei die Cycloalkylgruppe gegebenenfalls substituiert ist, eine C7-C15-Arylalkyl- oder Alkylarylgruppe, eine C6-C14-Arylgruppe, wobei die Arylgruppe-gegebenenfalls substituiert ist, eine heterocyclische Gruppe mit 5 oder 6 Atomen, die mindestens ein unter Sauerstoff, Stickstoff und Schwefel ausgewähltes Heteroatom enthält, wobei die heterocyclische Gruppe gegebenenfalls substituiert ist, eine Acylgruppe der allgemeinen Formel (VII):
    Figure 00700001
    oder eine Estergruppe der allgemeinen Formel (VIII):
    Figure 00700002
    worin R' die vorstehend gegebene Bedeutung hat, darstellt, R2und R3 gleich oder verschieden sind und ein Wasserstoffatom, eine geradekettige oder verzweigte C1-C18-Alkylgruppe, eine Phenylgruppe, eine heterocyclische Gruppe mit 5 oder 6 Atomen, die mindestens ein unter Sauerstoff, Stickstoff und Schwefel ausgewähltes Heteröatom enthält, wobei die heterocyclische Gruppe gegebenenfalls substituiert ist, darstellen,
    worin die C5-C18-Cycloalkylgruppen, die C6-C14-Arylgruppen und die heterocyclischen Gruppen mit 5 oder 6 Atomen mit Halogenatomen, ausgewählt unter Chlor und Brom, geradekettigen oder verzweigten C1-C18-Alkylgruppen, geradekettigen oder verzweigten C2-C18-Alkenylgruppen, geradekettigen oder verzweigten C2-C18-Alkinylgruppen, OH-Gruppen, NH-Gruppen, SH-Gruppen substituiert sind.
  2. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die C1-C18-Alkylgruppen Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, sec-Butyl, t-Butyl, t-Amyl, 2-Ethylhexyl, n-Octyl, 1,1,3,3-Tetramethylbutyl, n-Dodecyl, 1,1,7,7-Tetramethyloctyl oder n-Octadecyl sind.
  3. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die C2-C18-Alkenylgruppen Vinyl, Propylen, Butylen, Pentylen oder Hexylen sind.
  4. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die C2-C18-Alkinylgruppen Acetylen, Propin, Butin oder 2-Butin sind.
  5. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die gegebenenfalls substituierten C5-C18-Cycloalkylgruppen Cyclohexyl, Cyclopentyl oder Methylcyclohexyl sind.
  6. 2-(2'-Hydroxyphenyl) benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die C7-C15-Arylalkyl- oder Alkylarylgruppen Benzyl, 2-Phenylethyl oder 4-t-Butylbenzyl sind.
  7. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die gegebenenfalls substituierten C6-C14-Arylgruppen Phenyl, Naphthyl, Anthracenyl oder 2-Hydroxyphenyl sind.
  8. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die C1-C18-Alkoxygruppen Methoxy, Ethoxy, Propoxy oder n-Butoxy sind.
  9. 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach Anspruch 1, worin die gegebenenfalls substituierten heterocyclischen Gruppen mit 5 oder 6 Atomen Piperidin, Morpholin, Piperazin, Triazol, Tetramethylpiperidin, Pentamethylpiperidin, Tetramethylmorpholin, Pentamethylmorpholin oder 4-Hydroxytetramethylpiperidin sind.
  10. 2-(2'-Hydroxyphenyl)benzotriazol nach Anspruch 1 der Formel
    Figure 00720001
  11. 2-(2'-Hydroxyphenyl)benzotriazol nach Anspruch 1 der Formel
    Figure 00720002
  12. Verfahren zur Herstellung von 2-(2'-Hydroxyphenyl)benzotriazolen der allgemeinen Formel (I) nach einem der vorhergehenden Patentansprüche, welches umfaßt:
    (a) die Umsetzung eines 2-(2'-Hydroxyphenyl)benzotriazols der allgemeinen Formel (IX):
    Figure 00720003
    worin X und R die vorstehend definierten Bedeutungen haben, mit einem sekundären Amin der allgemeinen Formel (X):
    Figure 00720004
    worin R7 und R8 gleich oder verschieden sind, vorzugsweise gleich sind, und eine geradekettige Alkylgruppe mit 3 oder mehr Kohlenstoffatomen darstellen, in Gegenwart von Formaldehyd oder Paraformaldehyd und eines inerten organischen Lösungsmittels bei einer Temperatur im Bereich von 95°C bis 100°C während einer Dauer im Bereich von 40 Stunden bis 60 Stunden, wobei die Mannich-Base der allgemeinen Formel (XI) erhalten wird:
    Figure 00730001
    worin R, R7 und R8 die vorstehend definierte Bedeutung haben,
    (b) Umsetzen der in Stufe (a) erhaltenen Mannich-Base der allgemeinen Formel (XI) mit einem 2,4-Imidazolidindion der allgemeinen Formel (XII):
    Figure 00730002
    worin R1, R2 und R3 die vorstehend beschriebenen Bedeutungen haben, in Gegenwart eines alkalischen Katalysators und eines inerten organischen Lösungsmittels mit einem Siedepunkt von 160°C bei einer Temperatur im Bereich von 20°C bis 200°C während einer Dauer im Bereich von 20 Stunden bis 30 Stunden, wobei eine Lösung erhalten wird, aus der nach dem Abkühlen auf Raumtemperatur und Entfernen des Katalysators durch Filtration und-des Lösungsmittels durch Verdampfen die gewünschte Verbindung durch Kristallisation in Gegenwart eines inerten organischen Lösungsmittels isoliert wird, das unter Alkoholen, Monoalkylethern, geradekettigen oder cyclischen aliphatischen Kohlenwasserstoffen, aromatischen Kohlenwasserstoffen und chlorierten aromatischen Lösungsmitteln ausgewählt ist.
  13. Verfahren nach Anspruch 12, wobei die Stufe (a) in Gegenwart von Paraformaldehyd und n-Butanol durchgeführt wird.
  14. Verfahren nach Anspruch 12, wobei die in Stufe (b) verwendeten Katalysatoren Natriummethylat, Natriumhydroxid, Kaliumhydroxide, Lithiumhydroxid sind.
  15. Verfahren nach Anspruch 12, wobei die in Stufe (b) verwendeten inerten organischen Lösungsmittel mit einem Siedepunkt von 160°C 1,2,4-Trimethylbenzol oder 4-Isopropylbenzol sind.
  16. Verfahren nach Anspruch 12, wobei Stufe (b) bei einer Temperatur im Bereich von 40°C bis 170°C durchgeführt wird.
  17. Verfahren nach Anspruch 12, wobei die in Stufe (b) verwendeten Kristallisationslösungsmittel Methanol, 2-Methoxyethanol, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Toluol oder Chlorbenzol sind.
  18. Polymerzusammensetzungen, die ein organisches Polymer und eine wirksame Menge eines oder mehrerer 2-(2'-Hydroxyphenyl)-benzotriazole der allgemeinen Formel (I) nach einem der vorhergehenden Patentansprüche enthalten.
  19. Polymerzusammensetzungen nach Anspruch 18, wobei die 2-(2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) mit anderen Stabilisatoren kombiniert sind.
  20. Polymerzusammensetzungen nach Anspruch 18 oder 19, wobei das organische Polymer unter Polycarbonaten ausgewählt ist.
  21. Verwendung der (2'-Hydroxyphenyl)benzotriazole der allgemeinen Formel (I) nach einem der Ansprüche 1 bis 11 als Lichtstabilisatoren für organische Polymere.
  22. Verwendung der Polymerzusammensetzungen nach Anspruch 18 oder 19 zur Herstellung von Mehrschichtsystemen, wobei die obere Schicht einer Dicke von 10 bis 100 µm diese Zusammensetzungen enthält, während die innere Schicht eine Verbindung der allgemeinen Formel (I) nach einem der Ansprüche 1 bis 11 nicht oder in geringer Menge enthält.
  23. Verwendung der Polymerzusammensetzungen nach Anspruch 18 oder 19 als Überzugs- oder Anstrich-Zusammensetzungen.
EP19980955498 1997-10-30 1998-10-22 2-(2'-hydroxyphenyl)benzotriazole verwendbar als uv-stabilisatoren Expired - Lifetime EP1027348B1 (de)

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ITMI972436 1997-10-30
IT97MI002436A IT1295933B1 (it) 1997-10-30 1997-10-30 2-(2'-idrossifenil)benzotriazoli e procedimento per la loro preparazione
PCT/EP1998/006654 WO1999023093A1 (en) 1997-10-30 1998-10-22 2-(2'-hydroxyphenyl)benzotriazoles used as u.v. stabilisers

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WO1999023093A1 (en) 1999-05-14
ATE246187T1 (de) 2003-08-15
US6407254B1 (en) 2002-06-18
PT1027348E (pt) 2003-11-28
IT1295933B1 (it) 1999-05-28
DE69816851T2 (de) 2004-05-27
JP2001521936A (ja) 2001-11-13
DE69816851D1 (de) 2003-09-04
DK1027348T3 (da) 2003-11-17
EP1027348A1 (de) 2000-08-16
ITMI972436A1 (it) 1999-04-30

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